EP0714902A2 - Rhenium and aluminium compounds, their preparation and their use as catalysts - Google Patents

Rhenium and aluminium compounds, their preparation and their use as catalysts Download PDF

Info

Publication number
EP0714902A2
EP0714902A2 EP95402429A EP95402429A EP0714902A2 EP 0714902 A2 EP0714902 A2 EP 0714902A2 EP 95402429 A EP95402429 A EP 95402429A EP 95402429 A EP95402429 A EP 95402429A EP 0714902 A2 EP0714902 A2 EP 0714902A2
Authority
EP
European Patent Office
Prior art keywords
phenyl
compound
solvent
rhenium
butyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP95402429A
Other languages
German (de)
French (fr)
Other versions
EP0714902A3 (en
EP0714902B1 (en
Inventor
Dominique Commereuc
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
IFP Energies Nouvelles IFPEN
Original Assignee
IFP Energies Nouvelles IFPEN
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by IFP Energies Nouvelles IFPEN filed Critical IFP Energies Nouvelles IFPEN
Publication of EP0714902A2 publication Critical patent/EP0714902A2/en
Publication of EP0714902A3 publication Critical patent/EP0714902A3/en
Application granted granted Critical
Publication of EP0714902B1 publication Critical patent/EP0714902B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
    • C07F13/005—Compounds without a metal-carbon linkage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • B01J2531/31—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/74—Rhenium

Definitions

  • the present invention relates to new compounds of rhenium and aluminum, their preparation and their use as catalysts, in particular for the metathesis of olefins in homogeneous phase.
  • rhenium pentachloride ReCl 5 associated with tetrabutyltin (JA Moulijn et al., J. Chem. Soc. Chem. Comm., 1971, p. 1170), or with triethylaluminum in the presence of oxygen (Y. Uchida et al., Bull. Chem. Soc. Japan, vol.
  • the object of the present invention is to describe new compounds of rhenium and aluminum, soluble in hydrocarbon medium, and which are in themselves active for catalysis, and in particular for catalyzing the metathesis reaction, without qu 'it is necessary (in most cases) to add a co-catalyst to them.
  • R is a hydrocarbyl residue, for example alkyl, cycloalkyl, alkenyl, aryl, and aryl or cycloalkyl substituted by at least one group alkyl, R containing from 1 to 40 carbon atoms, preferably a hydrocarbyl residue of 2 to 30 carbon atoms, this residue possibly being substituted by at least one alkoxy group or by at least one halogen, L is the synthesis solvent, x is equal to 0 or 1 and n is an integer from 1 to 10.
  • R may be an ethyl, n-propyl, isopropyl, n-butyl, t residue -butyl, cyclohexyl, benzyl, diphenylmethyl, phenyl, methyl-2-phenyl, methyl-4-phenyl, methoxy-2-phenyl, methoxy-4-phenyl, dimethyl-2,6-phenyl, diisopropyl-2,6-phenyl , t-butyl-2-phenyl, t-butyl-2-methyl-4-phenyl, di-t-butyl-2,6-phenyl, di-t-butyl-2,6-methyl-4-phenyl, tri -t-butyl-2,4,6-phenyl, phenyl-2-phenyl, diphenyl-2,6-phenyl, fluoro-2-phenyl, fluoro-4-phenyl, penta
  • Solvent L will be defined later when describing a preparation process.
  • the stabilized compounds, inactive in catalysis, correspond to the general formula: O 3 Re (L ') - O- [Al (OR) (L) x -O] n -ReO 3 (L') (B)
  • L ′ is a stabilizing ligand chosen from compounds comprising at least one oxygen, sulfur, nitrogen, phosphorus or arsenic atom, for example an ether, such as diethyl ether, 1,2-dimethoxy- ethane or tetrahydrofuran, a sulfide such as tetrahydrothiophene, an amine, such as triethylamine, pyridine, bipyridine-2,2 'or N, N, N', N'-tetramethylethylenediamine, a phosphine, such as triphenylphosphine or bis- (diphenylphosphino) -1,2-ethane.
  • R, L, x and n were defined when expressing the
  • the identification of the stabilized compounds B allows a posteriori characterization of the compounds A: the formula of A is deduced from that of B by abstraction of the stabilizing ligand L '. Furthermore, by decoordination of L ′, compound A can be obtained from compound B.
  • the rhenium and aluminum compounds according to the invention are synthesized by reaction between the rhenium heptoxide Re 2 O 7 and at least one aluminum compound of formula (RO) q AlR ' r , where R is defined as above, R ′ is an alkyl residue containing from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms, for example methyl, ethyl, isobutyl, q and r are equal to 1 or 2 so that the sum q + r is equal to 3.
  • R is defined as above
  • R ′ is an alkyl residue containing from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms, for example methyl, ethyl, isobutyl
  • q and r are equal to 1 or 2 so that the sum q + r is equal to 3.
  • the reaction is carried out in a so-called synthetic solvent L, preferably anhydrous, chosen from the group consisting of hydrocarbons, aliphatic or aromatic, such as for example pentane, hexane, benzene, toluene, halogenated hydrocarbons, such as for example dichloromethane, chlorobenzene, ethers, such as, for example, diethyl ether, diisopropyl ether, dimethoxy-1,2-ethane, tetrahydrofuran or sulfides such as tetrahydrothiophene.
  • An ether is preferably used.
  • Said solvent L as defined can enter into the general formula of compounds A.
  • the molar ratio between the aluminum compound and the rhenium can be chosen from 0.2: 1 to 10: 1. Preferably a ratio of 0.5: 1 to 5: 1 is used.
  • the order of introduction of the reagents is not critical, however it is preferable to introduce the aluminum compound into the solution or suspension of rhenium heptoxide.
  • the preparation of the compound (RO) q AlR ' r is known to a person skilled in the art. Any process for the preparation of this compound is suitable, for example, by reaction of a compound AlR ' 3 with a compound ROH, R and R' being as defined above, the reaction advantageously taking place in a solvent L.
  • the compound thus prepared is brought into contact with rhenium heptoxide.
  • the compound thus prepared is isolated, then it is brought into contact with rhenium heptoxide under the conditions described by the invention.
  • the reagents used to form the compound (RO) q AlR ' r are simultaneously brought into contact with rhenium heptoxide, without there being any separation of the product (RO) q AlR' r .
  • the reaction temperature can be from -80 to +100 ° C, preferably from -30 to +80 ° C.
  • the solvent is advantageously removed at least in part (for example the solvent is evaporated under vacuum) and the residue (evaporation) is extracted with a solvent L 1 , for example preferably an aliphatic, aromatic hydrocarbon or cycloaliphatic, or alternatively a halogenated hydrocarbon or a nitro derivative, such as for example advantageously pentane, heptane, benzene or toluene.
  • the extraction solution is directly usable for catalysis, for example metathesis.
  • the solution obtained containing compound A is used directly as a catalytic composition.
  • a preliminary separation of the solvent is also possible in this case.
  • the ligand L ′ as defined above is added to it, and the stabilized compound B is separated by any usual method, for example by precipitation or by crystallization.
  • Another object of the present invention is the use of these new rhenium and aluminum compounds for the preparation of catalysts, and in particular of catalysts for the reaction of metathesis of olefins.
  • Compounds A can be used as such, in particular as catalysts in homogeneous phase in the solvent resulting from their preparation. This solvent can also be removed by evaporation to replace it with at least one other more advantageous solvent.
  • Compounds A can be used in metathesis in a solvent consisting of an aliphatic, cycloaliphatic or aromatic hydrocarbon, a halogenated hydrocarbon or a nitro derivative. Preferably, a hydrocarbon or a halogenated hydrocarbon is used.
  • cocatalyst having alkylating and / or Lewis acid properties.
  • This cocatalyst can be a compound of aluminum, boron, gallium, tin or lead.
  • the process for metathesis of olefins in the presence of the catalyst defined above takes place at a temperature of -20 to +200 ° C, preferably from 0 to +100 ° C, under pressure conditions such that the reactants are maintained at less in majority (more than 50%) in the liquid phase or in the condensed phase.
  • the olefins capable of being metathetized are monoolefins having from 2 to 30 carbon atoms, for example ethylene, propylene, butenes, pentenes, cycloolefins having from 3 to 20 carbon atoms, for example cyclopentene, cyclooctene, norbornene, polyolefins having from 4 to 30 carbon atoms, for example 1,4-hexadiene, 1,7-octadiene, cyclopolyolefins having from 5 to 30 carbon atoms, for example cyclooctadiene -1.5, norbornadiene, dicyclopentadiene.
  • olefins capable of being metathetized are monoolefins or polyolefins, linear or cyclic, carrying functional groups such as, for example, halogens or ester groups.
  • the process can also use in cometathesis a mixture of the above olefins.
  • a solution of 2 ml of triisobutylaluminum in 30 ml of pentane is introduced into a 250 ml flask placed under an argon atmosphere and fitted with a magnetic bar, and is then injected dropwise, with stirring and at room temperature. , a solution of 3.49 g of di-t-butyl-2,6-methyl-4-phenol in 40 ml of pentane. After approximately 30 hours of reaction, the pentane is evaporated under vacuum and the analysis of the remaining white solid indicates that it consists essentially of bis- (di-t-butyl-2,6-methyl-4-phenoxy) - isobutylaluminium.
  • the solvent is then evaporated under vacuum to obtain a gray-black solid mass, which is then extracted 5 times with 30 ml of pentane.
  • the pentane extraction solution has a reddish brown color and its evaporation to dryness gives 3.32 g of a brown powder containing the compound A1. This powder is redissolved in 30 ml of heptane.
  • the bis- (di-t-butyl-2,6-methyl-4-phenoxy) -isobutylaluminum is prepared according to the procedure described in Example 1.
  • a 250 ml flask placed under an argon atmosphere and provided with 'a magnetic bar is introduced 1.5 g of rhenium heptoxide Re 2 O 7 which is dissolved in 25 ml of tetrahydrofuran.
  • the solution is cooled in a dry ice-acetone bath and a solution of 3.24 g of bis- (di-t-butyl-2,6-methyl-4-phenoxy) -isobutylaluminum in 45 ml is added thereto in 30 minutes. tetrahydrofuran.
  • a solution of 2 ml of triisobutylaluminum in 15 ml of pentane is introduced into a 250 ml balloon placed under an argon atmosphere and fitted with a magnetic bar, and is then injected dropwise, with stirring and at room temperature.
  • a solution of 1.95 g of 2,6-diphenylphenol in a mixture of 15 ml of pentane and 20 ml of toluene is evaporated under vacuum and the residual white solid is recrystallized from toluene.
  • 1.32 g of product are obtained in the form of white crystals, the analysis of which indicates that they consist of bis- (diphenyl-2,6-phenoxy) -isobutylaluminium.
  • rhenium heptoxide Re 2 O 7 0.556 g are introduced into a 250 ml flask placed under an argon atmosphere and fitted with a magnetic bar, which is dissolved in 10 ml of tetrahydrofuran.
  • the solution is cooled in a dry ice-acetone bath and a solution of 1.32 g of bis- (diphenyl-2,6-phenoxy) -isobutylaluminum in 15 ml of tetrahydrofuran is added over 30 minutes.
  • the temperature is allowed to rise to ambient and the stirring is continued for a further 5 hours.
  • the solvent is then evaporated under vacuum to obtain a gray-black solid mass, which is then extracted with 15 ml of toluene.
  • the extraction solution has a dark brown color and is used directly in the metathesis catalysis of pentene-2.
  • the flask containing the extraction solution is immersed in a thermostatic bath at 25 ° C. Then injected into this solution 3 ml of pentene-2 (cis + trans mixture). After one hour of reaction, the conversion of pentene-2 is 3%. After 4 days of reaction, the conversion of pentene-2 is 29%.
  • the bis- (di-t-butyl-2,6-methyl-4-phenoxy) -isobutylaluminum is prepared according to the procedure described in Example 1.
  • 1 g of rhenium heptoxide Re 2 O 7 and 30 ml of diethyl ether are introduced.
  • the solution is cooled in a dry ice-acetone bath and a solution of 2.16 g of bis- (di-t-butyl-2,6-methyl-4-phenoxy) -isobutylaluminum in 30 ml is added over 5 minutes. of diethyl ether.
  • the temperature is allowed to rise to ambient and the stirring is continued for another 2 hours.
  • the solvent is then evaporated under vacuum to obtain a dark brown solid mass, which is then extracted 3 times with 30 ml of pentane.
  • the pentane extraction solution has a reddish brown color and its evaporation to dryness gives 2.66 g of a dark red powder. This powder is redissolved in 20 ml of heptane.
  • the bis- (di-t-butyl-2,6-methyl-4-phenoxy) -isobutylaluminum is prepared according to the procedure described in Example 1.
  • 1 g of rhenium heptoxide Re 2 O 7 and 15 ml of diisopropyl ether are introduced.
  • the solution is cooled in a dry ice-acetone bath and a solution of 2.16 g of bis- (di-t-butyl-2,6-methyl-4-phenoxy) -isobutylaluminum in 30 ml is added over 5 minutes. diisopropyl ether.
  • the temperature is allowed to rise to ambient and the stirring is continued for another 2 hours.
  • the solvent is then evaporated under vacuum to obtain a dark brown solid mass, which is then extracted 4 times with 20 ml of pentane.
  • the pentane extraction solution has a reddish brown color and its evaporation to dryness gives 2.48 g of a dark red powder. This powder is redissolved in 20 ml of heptane.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Polymerization Catalysts (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

New cpds. of formula O3Re-O-(Al(OR)(L)x-O)n-ReO3 (I) are claimed. R = 1-40C hydrocarbon gp.; n = 1-10; x = 0 or 1; L = the synthesis solvent.

Description

La présente invention concerne de nouveaux composés du rhénium et de l'aluminium, leur préparation et leur utilisation comme catalyseurs, en particulier pour la métathèse des oléfines en phase homogène.The present invention relates to new compounds of rhenium and aluminum, their preparation and their use as catalysts, in particular for the metathesis of olefins in homogeneous phase.

Les composés du rhénium solubles capables de catalyser en phase homogène la réaction de métathèse des oléfines sont très peu nombreux. Il est de plus indispensable, pour promouvoir leur activité, de les associer à un cocatalyseur, le plus souvent un composé de l'aluminium ou de l'étain, présentant des propriétés alkylantes et/ou d'acide de Lewis. On peut citer à titre d'exemple le pentachlorure de rhénium ReCl5, associé au tétrabutylétain (J.A. Moulijn et al., J. Chem. Soc. Chem. Comm., 1971, p. 1170), ou au triéthylaluminium en présence d'oxygène (Y. Uchida et al., Bull. Chem. Soc. Japan, vol. 45, 1972, p. 1158), ses dérivés tels que ReCl4(PPh3) et ReOCl3(PPh3)2 associés au dichloroéthylaluminium (brevet français 1 561 025), le rhénium pentacarbonyle chlorure Re(CO)5Cl associé au dichloroéthylaluminium (M.F. Farona et al., lnorg. Chem., vol. 15, 1976, p. 2129), le dirhéniumdécacarbonyle Re2(CO)10 en présence de dichloroisobutylaluminium comme cocatalyseur (S. Warwel et al., Makromol. Chem. Rapid Comm., vol. 4, 1983, p. 423), le méthyltrioxorhénium CH3ReO3 associé à un chloroalkylaluminium ou à un mélange de chlorure d'aluminium et de tétraméthylétain (W.A. Herrmann et al., Angew. Chem. Int. Ed. Engl., vol. 30, 1991, p. 1636, et vol. 27, 1988, p. 394).Very few rhenium compounds capable of catalyzing the metathesis reaction of olefins in a homogeneous phase. It is moreover essential, to promote their activity, to associate them with a cocatalyst, most often a compound of aluminum or tin, having alkylating properties and / or Lewis acid. By way of example, mention may be made of rhenium pentachloride ReCl 5 , associated with tetrabutyltin (JA Moulijn et al., J. Chem. Soc. Chem. Comm., 1971, p. 1170), or with triethylaluminum in the presence of oxygen (Y. Uchida et al., Bull. Chem. Soc. Japan, vol. 45, 1972, p. 1158), its derivatives such as ReCl 4 (PPh 3 ) and ReOCl 3 (PPh 3 ) 2 associated with dichloroethyl aluminum ( French patent 1,561,025), the rhenium pentacarbonyl chloride Re (CO) 5 Cl associated with dichloroethylaluminium (MF Farona et al. , lnorg. Chem., vol. 15, 1976, p. 2129), the dirheniumdecacarbonyl Re 2 (CO) 10 in the presence of dichloroisobutylaluminium as cocatalyst (S. Warwel et al., Makromol. Chem. Rapid Comm., Vol. 4, 1983, p. 423), methyltrioxorhenium CH 3 ReO 3 combined with a chloroalkylaluminium or with a mixture of chloride aluminum and tetramethyltin (WA Herrmann et al., Angew. Chem. Int. Ed. Engl., vol. 30, 1991, p. 1636, and vol. 27, 1988, p. 394).

L'objet de la présente invention est de décrire de nouveaux composés du rhénium et de l'aluminium, solubles en milieu hydrocarboné, et qui sont en eux-mêmes actifs pour la catalyse, et en particulier pour catalyser la réaction de métathèse, sans qu'il soit nécessaire (dans la plupart des cas) de leur adjoindre un cocatalyseur.The object of the present invention is to describe new compounds of rhenium and aluminum, soluble in hydrocarbon medium, and which are in themselves active for catalysis, and in particular for catalyzing the metathesis reaction, without qu 'it is necessary (in most cases) to add a co-catalyst to them.

Ces nouveaux composés du rhénium et de l'aluminium répondent à la formule générale :

        O3Re-O-[Al(OR)(L)x-O]n-ReO3     (A)

   où R est un reste hydrocarbyle, par exemple alkyle, cycloalkyle, alkényle, aryle, et aryle ou cycloalkyle substitués par au moins un groupe alkyle, R contenant de 1 à 40 atomes de carbone, de préférence un reste hydrocarbyle de 2 à 30 atomes de carbone, ce reste pouvant être substitué par au moins un groupe alkoxy ou par au moins un halogène, L est le solvant de synthèse, x est égal à 0 ou 1 et n est un nombre entier de 1 à 10. A titre d'exemple, et sans que la liste soit limitative, R peut être un reste éthyle, n-propyle, isopropyle, n-butyle, t-butyle, cyclohexyle, benzyle, diphénylméthyle, phényle, méthyl-2-phényle, méthyl-4-phényle, méthoxy-2-phényle, méthoxy-4-phényle, diméthyl-2,6-phényle, diisopropyl-2,6-phényle, t-butyl-2-phényle, t-butyl-2-méthyl-4-phényle, di-t-butyl-2,6-phényle, di-t-butyl-2,6-méthyl-4-phényle, tri-t-butyl-2,4,6-phényle, phényl-2-phényle, diphényl-2,6-phényle, fluoro-2-phényle, fluoro-4-phényle, pentafluorophényle.These new compounds of rhenium and aluminum correspond to the general formula:

O 3 Re-O- [Al (OR) (L) x -O] n -ReO 3 (A)

where R is a hydrocarbyl residue, for example alkyl, cycloalkyl, alkenyl, aryl, and aryl or cycloalkyl substituted by at least one group alkyl, R containing from 1 to 40 carbon atoms, preferably a hydrocarbyl residue of 2 to 30 carbon atoms, this residue possibly being substituted by at least one alkoxy group or by at least one halogen, L is the synthesis solvent, x is equal to 0 or 1 and n is an integer from 1 to 10. By way of example, and without the list being limiting, R may be an ethyl, n-propyl, isopropyl, n-butyl, t residue -butyl, cyclohexyl, benzyl, diphenylmethyl, phenyl, methyl-2-phenyl, methyl-4-phenyl, methoxy-2-phenyl, methoxy-4-phenyl, dimethyl-2,6-phenyl, diisopropyl-2,6-phenyl , t-butyl-2-phenyl, t-butyl-2-methyl-4-phenyl, di-t-butyl-2,6-phenyl, di-t-butyl-2,6-methyl-4-phenyl, tri -t-butyl-2,4,6-phenyl, phenyl-2-phenyl, diphenyl-2,6-phenyl, fluoro-2-phenyl, fluoro-4-phenyl, pentafluorophenyl.

Le solvant L sera défini plus loin lors de la description d'un procédé de préparation.Solvent L will be defined later when describing a preparation process.

L'activité catalytique de ces composés du rhénium et de l'aluminium (notamment en métathèse des oléfines) a pour conséquence leur instabilité lorsque l'on cherche à les isoler. Pour les caractériser, il est nécessaire de les stabiliser par addition, à la fin de leur synthèse, de ligands convenables. Les composés stabilisés, inactifs en catalyse, répondent à la formule générale :

        O3Re(L')-O-[Al(OR)(L)x-O]n-ReO3(L')     (B)

   où L' est un ligand stabilisant choisi parmi les composés comportant au moins un atome d'oxygène, de soufre, d'azote, de phosphore ou d'arsenic, par exemple un éther, comme le diéthyléther, le diméthoxy-1,2-éthane ou le tétrahydrofurane, un sulfure comme le tétrahydrothiophène, une amine, comme la triéthylamine, la pyridine, la bipyridine-2,2' ou la N,N,N',N'-tétraméthyléthylènediamine, une phosphine, comme la triphénylphosphine ou le bis-(diphénylphosphino)-1,2-éthane. R, L, x et n ont été définis lors de l'expression de la formule du composé A.The catalytic activity of these rhenium and aluminum compounds (especially in metathesis of olefins) results in their instability when one seeks to isolate them. To characterize them, it is necessary to stabilize them by adding, at the end of their synthesis, suitable ligands. The stabilized compounds, inactive in catalysis, correspond to the general formula:

O 3 Re (L ') - O- [Al (OR) (L) x -O] n -ReO 3 (L') (B)

where L ′ is a stabilizing ligand chosen from compounds comprising at least one oxygen, sulfur, nitrogen, phosphorus or arsenic atom, for example an ether, such as diethyl ether, 1,2-dimethoxy- ethane or tetrahydrofuran, a sulfide such as tetrahydrothiophene, an amine, such as triethylamine, pyridine, bipyridine-2,2 'or N, N, N', N'-tetramethylethylenediamine, a phosphine, such as triphenylphosphine or bis- (diphenylphosphino) -1,2-ethane. R, L, x and n were defined when expressing the formula for compound A.

L'identification des composés B stabilisés permet de caractériser a posteriori les composés A : la formule de A se déduit de celle de B par abstraction du ligand stabilisant L'. Par ailleurs, par décoordination de L', le composé A peut être obtenu à partir du composé B.The identification of the stabilized compounds B allows a posteriori characterization of the compounds A: the formula of A is deduced from that of B by abstraction of the stabilizing ligand L '. Furthermore, by decoordination of L ′, compound A can be obtained from compound B.

Les composés de rhénium et d'aluminium selon l'invention sont synthétisés par réaction entre l'heptoxyde de rhénium Re2O7 et au moins un composé de l'aluminium de formule (RO)qAlR'r, où R est défini comme ci-dessus, R' est un reste alkyle contenant de 1 à 20 atomes de carbone, de préférence de 1 à 6 atomes de carbone, par exemple méthyle, éthyle, isobutyle, q et r sont égaux à 1 ou 2 de telle façon que la somme q + r soit égale à 3.The rhenium and aluminum compounds according to the invention are synthesized by reaction between the rhenium heptoxide Re 2 O 7 and at least one aluminum compound of formula (RO) q AlR ' r , where R is defined as above, R ′ is an alkyl residue containing from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms, for example methyl, ethyl, isobutyl, q and r are equal to 1 or 2 so that the sum q + r is equal to 3.

La réaction est effectuée dans un solvant L dit de synthèse, de préférence anhydre, choisi dans le groupe constitué par les hydrocarbures, aliphatiques ou aromatiques, comme par exemple le pentane, l'hexane, le benzène, le toluène, les hydrocarbures halogénés, comme par exemple le dichlorométhane, le chlorobenzène, les éthers, comme par exemple le diéthyléther, le diisopropyléther, le diméthoxy-1,2-éthane, le tétrahydrofurane ou les sulfures comme le tétrahydrothiophène. On utilise de préférence un éther. Ledit solvant L tel que défini peut entrer dans la formule générale des composés A.The reaction is carried out in a so-called synthetic solvent L, preferably anhydrous, chosen from the group consisting of hydrocarbons, aliphatic or aromatic, such as for example pentane, hexane, benzene, toluene, halogenated hydrocarbons, such as for example dichloromethane, chlorobenzene, ethers, such as, for example, diethyl ether, diisopropyl ether, dimethoxy-1,2-ethane, tetrahydrofuran or sulfides such as tetrahydrothiophene. An ether is preferably used. Said solvent L as defined can enter into the general formula of compounds A.

Le rapport molaire entre le composé d'aluminium et le rhénium peut être choisi de 0,2:1 à 10:1. On utilise de préférence un rapport de 0,5:1 à 5:1. L'ordre d'introduction des réactifs n'est pas critique, cependant il est préférable d'introduire le composé d'aluminium dans la solution ou la suspension d'heptoxyde de rhénium.The molar ratio between the aluminum compound and the rhenium can be chosen from 0.2: 1 to 10: 1. Preferably a ratio of 0.5: 1 to 5: 1 is used. The order of introduction of the reagents is not critical, however it is preferable to introduce the aluminum compound into the solution or suspension of rhenium heptoxide.

La préparation du composé (RO)qAlR'r est connue de l'homme du métier. Tout procédé de préparation de ce composé convient, par exemple, par réaction d'un composé AlR'3 sur un composé ROH, R et R' étant tels que précédemment définis, la réaction ayant lieu avantageusement dans un solvant L. Le composé ainsi préparé est mis au contact de l'heptoxyde de rhénium. De façon générale, le composé ainsi préparé est isolé, puis est mis au contact de l'heptoxyde de rhénium dans les conditions décrites par l'invention.The preparation of the compound (RO) q AlR ' r is known to a person skilled in the art. Any process for the preparation of this compound is suitable, for example, by reaction of a compound AlR ' 3 with a compound ROH, R and R' being as defined above, the reaction advantageously taking place in a solvent L. The compound thus prepared is brought into contact with rhenium heptoxide. In general, the compound thus prepared is isolated, then it is brought into contact with rhenium heptoxide under the conditions described by the invention.

Dans un autre mode de réalisation, les réactifs utilisés pour former le composé (RO)qAlR'r sont simultanément mis au contact de l'heptoxyde de rhénium, sans qu'il y ait donc séparation du produit (RO)qAlR'r.In another embodiment, the reagents used to form the compound (RO) q AlR ' r are simultaneously brought into contact with rhenium heptoxide, without there being any separation of the product (RO) q AlR' r .

La température de réaction peut être de -80 à +100 °C, de préférence de -30 à +80 °C. Lorsque la réaction est terminée, on élimine avantageusement au moins en partie le solvant (par exemple on évapore le solvant sous vide) et le résidu (d'évaporation) est extrait par un solvant L1, par exemple de préférence un hydrocarbure aliphatique, aromatique ou cycloaliphatique, ou encore un hydrocarbure halogéné ou un dérivé nitré, comme par exemple avantageusement le pentane, l'heptane, le benzène ou le toluène. La solution d'extraction est directement utilisable pour la catalyse, par exemple de métathèse.The reaction temperature can be from -80 to +100 ° C, preferably from -30 to +80 ° C. When the reaction is complete, the solvent is advantageously removed at least in part (for example the solvent is evaporated under vacuum) and the residue (evaporation) is extracted with a solvent L 1 , for example preferably an aliphatic, aromatic hydrocarbon or cycloaliphatic, or alternatively a halogenated hydrocarbon or a nitro derivative, such as for example advantageously pentane, heptane, benzene or toluene. The extraction solution is directly usable for catalysis, for example metathesis.

Selon une variante, la solution obtenue contenant le composé A est directement utilisée comme composition catalytique. Une séparation préalable du solvant est également possible dans ce cas.According to a variant, the solution obtained containing compound A is used directly as a catalytic composition. A preliminary separation of the solvent is also possible in this case.

Si on souhaite isoler un composé stable B qui permette de caractériser a posteriori le composé A présent dans la solution d'extraction, on ajoute à celle-ci le ligand L' tel que défini ci-dessus, et on sépare le composé stabilisé B par toute méthode habituelle, par exemple par précipitation ou par cristallisation.If it is desired to isolate a stable compound B which makes it possible to characterize a posteriori the compound A present in the extraction solution, the ligand L ′ as defined above is added to it, and the stabilized compound B is separated by any usual method, for example by precipitation or by crystallization.

Un autre objet de la présente invention est l'utilisation de ces nouveaux composés de rhénium et d'aluminium pour la préparation de catalyseurs, et en particulier de catalyseurs pour la réaction de métathèse des oléfines.Another object of the present invention is the use of these new rhenium and aluminum compounds for the preparation of catalysts, and in particular of catalysts for the reaction of metathesis of olefins.

Les composés A sont utilisables tels quels en particulier comme catalyseurs en phase homogène dans le solvant résultant de leur préparation. On peut aussi éliminer ce solvant par évaporation pour le remplacer par au moins un autre solvant plus avantageux. Les composés A peuvent être mis en oeuvre dans la métathèse dans un solvant constitué par un hydrocarbure aliphatique, cycloaliphatique ou aromatique, un hydrocarbure halogéné ou un dérivé nitré. On utilise de préférence un hydrocarbure ou un hydrocarbure halogéné.Compounds A can be used as such, in particular as catalysts in homogeneous phase in the solvent resulting from their preparation. This solvent can also be removed by evaporation to replace it with at least one other more advantageous solvent. Compounds A can be used in metathesis in a solvent consisting of an aliphatic, cycloaliphatic or aromatic hydrocarbon, a halogenated hydrocarbon or a nitro derivative. Preferably, a hydrocarbon or a halogenated hydrocarbon is used.

Il est possible d'ajouter au composé A, bien que ce ne soit pas indispensable, au moins un cocatalyseur présentant des propriétés alkylantes et/ou d'acide de Lewis. Ce cocatalyseur peut être un composé d'aluminium, de bore, de gallium, d'étain ou de plomb. On peut citer à titre d'exemple, et sans que la liste soit limitative, le trichlorure d'aluminium, le tribromure d'aluminium, le dichloroéthylaluminium, le chlorodiéthylaluminium, le triéthylaluminium, le méthylaluminoxane, l'isobutylaluminoxane, le trifluorure de bore, le trichlorure de gallium, le tribromure de gallium, le tétraméthylétain, le tétraéthylétain, le tétrabutylétain, le tétraéthylplomb. On peut aussi utiliser ces divers composés en mélange entre eux.It is possible to add to compound A, although it is not essential, at least one cocatalyst having alkylating and / or Lewis acid properties. This cocatalyst can be a compound of aluminum, boron, gallium, tin or lead. Mention may be made, by way of example, and without the list being exhaustive, of aluminum trichloride, aluminum tribromide, dichloroethylaluminum, chlorodiethylaluminum, triethylaluminum, methylaluminoxane, isobutylaluminoxane, boron trifluoride, gallium trichloride, gallium tribromide, tetramethyltin, tetraethyltin, tetrabutyltin, tetraethyl lead. These various compounds can also be used in admixture with one another.

Le procédé de métathèse des oléfines en présence du catalyseur défini ci-dessus se déroule à une température de -20 à +200 °C, de préférence de 0 à +100 °C, dans des conditions de pression telles que les réactifs soient maintenus au moins en majorité (plus de 50 %) en phase liquide ou en phase condensée.The process for metathesis of olefins in the presence of the catalyst defined above takes place at a temperature of -20 to +200 ° C, preferably from 0 to +100 ° C, under pressure conditions such that the reactants are maintained at less in majority (more than 50%) in the liquid phase or in the condensed phase.

Les oléfines susceptibles d'être métathétisées sont des monooléfines ayant de 2 à 30 atomes de carbone, par exemple l'éthylène, le propylène, les butènes, les pentènes, des cyclooléfines ayant de 3 à 20 atomes de carbone, par exemple le cyclopentène, le cyclooctène, le norbornène, des polyoléfines ayant de 4 à 30 atomes de carbone, par exemple l'hexadiène-1,4, l'octadiène-1,7, des cyclopolyoléfines ayant de 5 à 30 atomes de carbone, par exemple le cyclooctadiène-1,5, le norbornadiène, le dicyclopentadiène.The olefins capable of being metathetized are monoolefins having from 2 to 30 carbon atoms, for example ethylene, propylene, butenes, pentenes, cycloolefins having from 3 to 20 carbon atoms, for example cyclopentene, cyclooctene, norbornene, polyolefins having from 4 to 30 carbon atoms, for example 1,4-hexadiene, 1,7-octadiene, cyclopolyolefins having from 5 to 30 carbon atoms, for example cyclooctadiene -1.5, norbornadiene, dicyclopentadiene.

D'autres oléfines susceptibles d'être métathétisées sont les monooléfines ou les polyoléfines, linéaires ou cycliques, portant des groupes fonctionnels comme par exemple des halogènes ou des groupes ester. Le procédé peut également mettre en oeuvre en cométathèse un mélange des oléfines précédentes.Other olefins capable of being metathetized are monoolefins or polyolefins, linear or cyclic, carrying functional groups such as, for example, halogens or ester groups. The process can also use in cometathesis a mixture of the above olefins.

Les exemples suivants illustrent l'invention sans en limiter la portée.The following examples illustrate the invention without limiting its scope.

EXEMPLE 1EXAMPLE 1 Préparation du bis-(di-t-butyl-2,6-méthyl-4-phénoxy)-isobutylaluminium : Preparation of bis- (di-t-butyl-2,6-methyl-4-phenoxy) -isobutylaluminium :

Dans un ballon de 250 ml placé sous atmosphère d'argon et muni d'un barreau magnétique, on introduit une solution de 2 ml de triisobutylaluminium dans 30 ml de pentane, puis on injecte goutte-à-goutte, sous agitation et à température ambiante, une solution de 3,49 g de di-t-butyl-2,6-méthyl-4-phénol dans 40 ml de pentane. Après environ 30 heures de réaction, le pentane est évaporé sous vide et l'analyse du solide blanc restant indique qu'il est constitué essentiellement par le bis-(di-t-butyl-2,6-méthyl-4-phénoxy)-isobutylaluminium.A solution of 2 ml of triisobutylaluminum in 30 ml of pentane is introduced into a 250 ml flask placed under an argon atmosphere and fitted with a magnetic bar, and is then injected dropwise, with stirring and at room temperature. , a solution of 3.49 g of di-t-butyl-2,6-methyl-4-phenol in 40 ml of pentane. After approximately 30 hours of reaction, the pentane is evaporated under vacuum and the analysis of the remaining white solid indicates that it consists essentially of bis- (di-t-butyl-2,6-methyl-4-phenoxy) - isobutylaluminium.

Préparation du catalyseur (composé A1) : Preparation of the catalyst (compound A1) :

Dans un ballon de 250 ml placé sous atmosphère d'argon et muni d'un barreau magnétique, on introduit 2,75 g d'heptoxyde de rhénium Re2O7 que l'on dissout dans 40 ml de tétrahydrofurane (THF). On refroidit la solution dans un bain de carboglace-acétone et on y ajoute en 30 minutes une solution de 2,97 g de bis-(di-t-butyl-2,6-méthyl-4-phénoxy)isobutylaluminium dans 50 ml de tétrahydrofurane. Ceci correspond à un rapport molaire Al:Re = 0,5:1. A la fin de l'addition, on laisse la température remonter à l'ambiante et on poursuit l'agitation pendant encore 2 heures. On évapore alors le solvant sous vide pour obtenir une masse solide gris-noir, que l'on extrait ensuite 5 fois par 30 ml de pentane. La solution d'extraction au pentane a une couleur brun-rouge et son évaporation à sec donne 3,32 g d'une poudre brune contenant le composé A1. Cette poudre est remise en solution dans 30 ml d'heptane.2.75 g of rhenium heptoxide Re 2 O 7 are introduced into a 250 ml flask placed under an argon atmosphere and fitted with a magnetic bar, which is dissolved in 40 ml of tetrahydrofuran (THF). The solution is cooled in a dry ice-acetone bath and a solution of 2.97 g of bis- (di-t-butyl-2,6-methyl-4-phenoxy) isobutylaluminum in 50 ml of solution is added over 30 minutes. tetrahydrofuran. This corresponds to an Al: Re molar ratio = 0.5: 1. At the end of the addition, the temperature is allowed to rise to ambient and the stirring is continued for another 2 hours. The solvent is then evaporated under vacuum to obtain a gray-black solid mass, which is then extracted 5 times with 30 ml of pentane. The pentane extraction solution has a reddish brown color and its evaporation to dryness gives 3.32 g of a brown powder containing the compound A1. This powder is redissolved in 30 ml of heptane.

Caractérisation du catalyseur (composé B1) : Characterization of the catalyst (compound B1) :

On prélève 4,5 ml de la solution dans l'heptane du composé A1 préparé ci-dessus. On évapore à sec le solvant et on reprend par 10 ml de toluène. On ajoute à cette solution 0,11 g de bipyridine-2,2' (bipy) dissous dans 3 ml de toluène. Par refroidissement à -20 °C, on obtient 0,1 g du composé B1 sous forme de microcristaux noirs. Analyse par RMN 1H (CD2Cl2) : δ [C(CH3)3] = 1,40 (s), δ (p-CH3) = 2,23, δ (C6H2) = 6,95, δ (bipy coordiné) = 7,32-7,81-8,41-8,64 ppm. Analyse élémentaire : C=47,46; H=5,66; N=3,17; Al=4,33; Re=26,4 % poids, calculé pour B1 : O3Re(bipy)-O-[Al(OC6H2-CH3-(t-C4H9)2)(THF)-O]2-ReO3(bipy) : C=47,54; H=5,33; N=3,82; Al=3,69; Re=25,4 % poids. On en déduit que le composé A1 préparé ci-dessus répond à la formule : O3Re-O-[Al(OC6H2-CH3-(t-C4H9)2)(THF)-O]2-ReO3.4.5 ml of the heptane solution of compound A1 prepared above are taken. The solvent is evaporated to dryness and the residue is taken up in 10 ml of toluene. 0.11 g of bipyridine-2,2 '(bipy) dissolved in 3 ml of toluene is added to this solution. By cooling to -20 ° C, 0.1 g of compound B1 is obtained in the form of black microcrystals. Analysis by 1 H NMR (CD 2 Cl 2 ): δ [C (CH 3 ) 3 ] = 1.40 (s), δ (p-CH 3 ) = 2.23, δ (C 6 H 2 ) = 6 , 95, δ (coordinated bipy) = 7.32-7.81-8.41-8.64 ppm. Elementary analysis: C = 47.46; H = 5.66; N = 3.17; Al = 4.33; Re = 26.4% by weight, calculated for B1: O 3 Re (bipy) -O- [Al (OC 6 H 2 -CH 3 - (tC 4 H 9 ) 2 ) (THF) -O] 2 -ReO 3 (bipy): C = 47.54; H = 5.33; N = 3.82; Al = 3.69; Re = 25.4% by weight. We deduce that the compound A1 prepared above corresponds to the formula: O 3 Re-O- [Al (OC 6 H 2 -CH 3 - (tC 4 H 9 ) 2 ) (THF) -O] 2 -ReO 3 .

EXEMPLE 2EXAMPLE 2 Utilisation du composé A1 en catalyse de métathèse du pentène-2 : Use of compound A1 in metathesis catalysis of pentene-2 :

On prélève 6,3 ml de la solution dans l'heptane du composé A1 préparé dans l'exemple 1, que l'on transfère dans un ballon de 100 ml placé sous atmosphère d'argon et équipé d'un barreau magnétique. On y ajoute 14 ml d'heptane et on plonge le ballon dans un bain thermostatique à 25 °C. On injecte alors dans cette solution 5 ml de pentène-2 (mélange cis + trans). Après une heure de réaction, la conversion du pentène-2 est de 50 %. La réaction est donc complète puisque la conversion maximum à l'équilibre thermodynamique est de 50 %. Les produits sont constitués uniquement par les butènes-2 cis et trans et les hexènes-3 cis et trans, dans un rapport molaire butènes : hexènes = 1:1.6.3 ml of the heptane solution of compound A1 prepared in Example 1 are taken, which is transferred to a 100 ml flask placed under an argon atmosphere and equipped with a magnetic bar. 14 ml of heptane are added thereto and the flask is immersed in a thermostatic bath at 25 ° C. Then injected into this solution 5 ml of pentene-2 (cis + trans mixture). After one hour of reaction, the conversion of pentene-2 is 50%. The reaction is therefore complete since the maximum conversion at thermodynamic equilibrium is 50%. The products consist solely of cis and trans butenes-2 and cis and trans hexenes-3, in a butene: hexene molar ratio = 1: 1.

EXEMPLE 3EXAMPLE 3 Préparation du catalyseur (composé A2) : Preparation of the catalyst (compound A2) :

Le bis-(di-t-butyl-2,6-méthyl-4-phénoxy)-isobutylaluminium est préparé selon le mode opératoire décrit dans l'exemple 1. Dans un ballon de 250 ml placé sous atmosphère d'argon et muni d'un barreau magnétique, on introduit 1,5 g d'heptoxyde de rhénium Re2O7 que l'on dissout dans 25 ml de tétrahydrofurane. On refroidit la solution dans un bain de carboglace-acétone et on y ajoute en 30 minutes une solution de 3,24 g de bis-(di-t-butyl-2,6-méthyl-4-phénoxy)-isobutylaluminium dans 45 ml de tétrahydrofurane. Ceci correspond à un rapport molaire Al:Re = 1:1. A la fin de l'addition, on laisse la température remonter à l'ambiante et on poursuit l'agitation pendant encore 2 heures. On évapore alors le solvant sous vide pour obtenir une masse solide gris-noir, que l'on extrait ensuite 5 fois par 30 ml de pentane. La solution d'extraction au pentane a une couleur brun-rouge et son évaporation à sec donne 3,57 g d'une poudre brun foncé contenant le composé A2. Cette poudre est remise en solution dans 30 ml d'heptane.The bis- (di-t-butyl-2,6-methyl-4-phenoxy) -isobutylaluminum is prepared according to the procedure described in Example 1. In a 250 ml flask placed under an argon atmosphere and provided with 'a magnetic bar is introduced 1.5 g of rhenium heptoxide Re 2 O 7 which is dissolved in 25 ml of tetrahydrofuran. The solution is cooled in a dry ice-acetone bath and a solution of 3.24 g of bis- (di-t-butyl-2,6-methyl-4-phenoxy) -isobutylaluminum in 45 ml is added thereto in 30 minutes. tetrahydrofuran. This corresponds to a molar ratio Al: Re = 1: 1. At the end of the addition, the temperature is allowed to rise to ambient and the stirring is continued for another 2 hours. The solvent is then evaporated under vacuum to obtain a gray-black solid mass, which is then extracted 5 times with 30 ml of pentane. The pentane extraction solution has a reddish brown color and its evaporation to dryness gives 3.57 g of a dark brown powder containing the compound A2. This powder is redissolved in 30 ml of heptane.

Caractérisation du catalyseur (composé B2) : Characterization of the catalyst (compound B2) :

On prélève 11 ml de la solution dans l'heptane du composé A2 préparé ci-dessus. On évapore à sec le solvant et on reprend par 5 ml de toluène. On ajoute à cette solution 0,41 g de bipyridine-2,2' dissous dans 5 ml de toluène. Par refroidissement à -20 °C, on obtient 0,2 g du composé B2 sous forme de microcristaux noirs. Analyse par RMN 1H (CD2Cl2) : δ [C(CH3)3] = 1,46 (s), δ (p-CH3) = 2,29, δ (C6H2) = 7,01, δ (bipy coordiné) = 7,85-8,46-8,68 ppm. Analyse élémentaire : C=51,57; H=6,22; N=3,52 % poids, calculé pour B2 : O3Re(bipy)-O-[Al(OC6H2-CH3-(t-C4H9)2)(THF)-O]3-ReO3(bipy) : C=51,39; H=6,06; N=3,11 % poids. On en déduit que le composé A2 préparé ci-dessus répond à la formule : O3Re-O-[Al(OC6H2-CH3-(t-C4H9)2)(THF)-O]3-ReO3.11 ml of the heptane solution of the compound A2 prepared above are taken. The solvent is evaporated to dryness and the residue is taken up in 5 ml of toluene. 0.41 g of bipyridine-2,2 'dissolved in 5 ml of toluene is added to this solution. By cooling to -20 ° C, 0.2 g of compound B2 is obtained in the form of black microcrystals. 1 H NMR analysis (CD 2 Cl 2 ): δ [C (CH 3 ) 3 ] = 1.46 (s), δ (p-CH 3 ) = 2.29, δ (C 6 H 2 ) = 7 , 01, δ (coordinated bipy) = 7.85-8.46-8.68 ppm. Elementary analysis: C = 51.57; H = 6.22; N = 3.52% weight, calculated for B2: O 3 Re (bipy) -O- [Al (OC 6 H 2 -CH 3 - (tC 4 H 9 ) 2 ) (THF) -O] 3 -ReO 3 (bipy): C = 51.39; H = 6.06; N = 3.11% by weight. We deduce that the compound A2 prepared above corresponds to the formula: O 3 Re-O- [Al (OC 6 H 2 -CH 3 - (tC 4 H 9 ) 2 ) (THF) -O] 3 -ReO 3 .

EXEMPLE 4EXAMPLE 4 Utilisation du composé A2 en catalyse de métathèse du pentène-2 : Use of compound A2 in metathesis catalysis of pentene-2 :

On prélève 3 ml de la solution dans l'heptane du composé A2 préparé dans l'exemple 3, que l'on transfère dans un ballon de 100 ml placé sous atmosphère d'argon et équipé d'un barreau magnétique. On y ajoute 20 ml d'heptane et on plonge le ballon dans un bain thermostatique à 25 °C. On injecte alors dans cette solution 5 ml de pentène-2 (mélange cis + trans). Après une heure de réaction, la conversion du pentène-2 est de 38 % (la conversion maximum à l'équilibre thermodynamique est de 50 %). Les produits sont constitués uniquement par les butènes-2 cis et trans et les hexènes-3 cis et trans, dans un rapport molaire butènes : hexènes = 1:1.3 ml of the heptane solution of the compound A2 prepared in Example 3 are taken, which is transferred to a 100 ml flask placed under an argon atmosphere and equipped with a magnetic bar. 20 ml of heptane are added thereto and the flask is immersed in a thermostatic bath at 25 ° C. Then injected into this solution 5 ml of pentene-2 (cis + trans mixture). After one hour of reaction, the conversion of pentene-2 is 38% (the maximum conversion at thermodynamic equilibrium is 50%). The products consist solely of cis and trans butenes-2 and cis and trans hexenes-3, in a butene: hexene molar ratio = 1: 1.

EXEMPLE 5EXAMPLE 5 Utilisation du composé A2 en catalyse de métathèse du pentène-2 : Use of compound A2 in metathesis catalysis of pentene-2 :

On prélève 3,7 ml de la solution dans l'heptane du composé A2 préparé dans l'exemple 3, que l'on transfère dans un ballon de 100 ml placé sous atmosphère d'argon et équipé d'un barreau magnétique. On évapore l'heptane à sec sous vide et on redissout le solide résiduel dans 20 ml de chlorobenzène. On plonge le ballon dans un bain thermostatique à 25 °C. On injecte alors dans cette solution 5 ml de pentène-2 (mélange cis + trans). Après une heure de réaction, la conversion du pentène-2 est de 50 % (la conversion maximum à l'équilibre thermodynamique est de 50 %). Les produits sont constitués uniquement par les butènes-2 cis et trans et les hexènes-3 cis et trans, dans un rapport molaire butènes : hexènes = 1:1.3.7 ml of the heptane solution of the compound A2 prepared in Example 3 are taken, which is transferred to a 100 ml flask placed under an argon atmosphere and equipped with a magnetic bar. The heptane is evaporated to dryness under vacuum and the residual solid is redissolved in 20 ml of chlorobenzene. The balloon is immersed in a thermostatic bath at 25 ° C. Then injected into this solution 5 ml of pentene-2 (cis + trans mixture). After one hour of reaction, the conversion of pentene-2 is 50% (the maximum conversion at thermodynamic equilibrium is 50%). The products consist solely of cis and trans butenes-2 and cis and trans hexenes-3, in a butene: hexene molar ratio = 1: 1.

EXEMPLE 6EXAMPLE 6 Utilisation du composé A2 en catalyse de métathèse de l'oléate de méthyle :Use of compound A2 in the metathesis catalysis of methyl oleate:

On prélève 3 ml de la solution dans l'heptane du composé A2 préparé dans l'exemple 3, que l'on transfère dans un ballon de 100 ml placé sous atmosphère d'argon et équipé d'un barreau magnétique. On y ajoute 20 ml d'heptane et on plonge le ballon dans un bain thermostatique à 25 °C. On injecte alors dans cette solution 5 ml d'oléate de méthyle. Après une heure de réaction, la conversion de l'oléate est de 16 %.3 ml of the heptane solution of the compound A2 prepared in Example 3 are taken, which is transferred to a 100 ml flask placed under an argon atmosphere and equipped with a magnetic bar. 20 ml of heptane are added thereto and the flask is immersed in a thermostatic bath at 25 ° C. 5 ml of methyl oleate are then injected into this solution. After one hour of reaction, the conversion of the oleate is 16%.

EXEMPLE 7EXAMPLE 7 Utilisation du composé A2 en catalyse de polymérisation du cyclopentène par ouverture de cycle (polymérisation par métathèse) : Use of compound A2 in catalysis for the polymerization of cyclopentene by ring opening (polymerization by metathesis) :

Dans un ballon de 100 ml placé sous atmosphère d'argon et équipé d'un barreau magnétique on introduit 20 ml d'heptane et on plonge le ballon dans un bain thermostatique à 25 °C. On injecte alors 5 ml de cyclopentène, puis 3 ml de la solution dans l'heptane du composé A2 préparé dans l'exemple 3. Après 4 minutes de réaction, la viscosité du milieu réactionnel a fortement augmenté. Après 1,5 heure, l'heptane est évaporé sous vide, puis le produit est repris au benzène et le polymère est précipité au méthanol. On recueille 2,14 g de polymère.20 ml of heptane are introduced into a 100 ml balloon placed under an argon atmosphere and equipped with a magnetic bar and the balloon is immersed in a thermostatic bath at 25 ° C. 5 ml of cyclopentene are then injected, then 3 ml of the heptane solution of compound A2 prepared in Example 3. After 4 minutes of reaction, the viscosity of the reaction medium has greatly increased. After 1.5 hours, the heptane is evaporated under vacuum, then the product is taken up in benzene and the polymer is precipitated with methanol. 2.14 g of polymer are collected.

EXEMPLE 8EXAMPLE 8 Utilisation du composé A2 en catalyse de polymérisation du norbornène par ouverture de cycle : Use of compound A2 in the polymerization of norbornene polymerization by ring opening :

Dans un ballon de 100 ml placé sous atmosphère d'argon et équipé d'un barreau magnétique on introduit 5 ml d'heptane et on plonge le ballon dans un bain thermostatique à 25 °C. On injecte alors 0,97 g de norbornène, puis 3,5 ml de la solution dans l'heptane du composé A2 préparé dans l'exemple 3. Après 30 secondes de réaction, le milieu réactionnel est pris en masse.In a 100 ml flask placed under an argon atmosphere and equipped with a magnetic bar, 5 ml of heptane are introduced and the flask is immersed in a thermostatic bath at 25 ° C. 0.97 g of norbornene is then injected, then 3.5 ml of the heptane solution of compound A2 prepared in Example 3. After 30 seconds of reaction, the reaction medium is solidified.

EXEMPLE 9EXAMPLE 9

Dans un ballon de 250 ml placé sous atmosphère d'argon et muni d'un barreau magnétique, on introduit une solution de 2 ml de triisobutylaluminium dans 15 ml de pentane, puis on injecte goutte-à-goutte, sous agitation et à température ambiante, une solution de 1,95 g de diphényl-2,6-phénol dans un mélange de 15 ml de pentane et 20 ml de toluène. Après environ 30 heures de réaction, le solvant est évaporé sous vide et le solide blanc résiduel est recristallisé dans le toluène. On obtient 1,32 g de produit sous forme de cristaux blancs dont l'analyse indique qu'il sont constitués par le bis-(diphényl-2,6-phénoxy)-isobutylaluminium.A solution of 2 ml of triisobutylaluminum in 15 ml of pentane is introduced into a 250 ml balloon placed under an argon atmosphere and fitted with a magnetic bar, and is then injected dropwise, with stirring and at room temperature. , a solution of 1.95 g of 2,6-diphenylphenol in a mixture of 15 ml of pentane and 20 ml of toluene. After approximately 30 hours of reaction, the solvent is evaporated under vacuum and the residual white solid is recrystallized from toluene. 1.32 g of product are obtained in the form of white crystals, the analysis of which indicates that they consist of bis- (diphenyl-2,6-phenoxy) -isobutylaluminium.

Dans un ballon de 250 ml placé sous atmosphère d'argon et muni d'un barreau magnétique, on introduit 0,556 g d'heptoxyde de rhénium Re2O7 que l'on dissout dans 10 ml de tétrahydrofurane. On refroidit la solution dans un bain de carboglace-acétone et on y ajoute en 30 minutes une solution de 1,32 g de bis-(diphényl-2,6-phénoxy)-isobutylaluminium dans 15 ml de tétrahydrofurane. A la fin de l'addition, on laisse la température remonter à l'ambiante et on poursuit l'agitation pendant encore 5 heures. On évapore alors le solvant sous vide pour obtenir une masse solide gris-noir, que l'on extrait ensuite par 15 ml de toluène. La solution d'extraction a une couleur brun foncé et est directement utilisée en catalyse de métathèse du pentène-2.0.556 g of rhenium heptoxide Re 2 O 7 are introduced into a 250 ml flask placed under an argon atmosphere and fitted with a magnetic bar, which is dissolved in 10 ml of tetrahydrofuran. The solution is cooled in a dry ice-acetone bath and a solution of 1.32 g of bis- (diphenyl-2,6-phenoxy) -isobutylaluminum in 15 ml of tetrahydrofuran is added over 30 minutes. At the end of the addition, the temperature is allowed to rise to ambient and the stirring is continued for a further 5 hours. The solvent is then evaporated under vacuum to obtain a gray-black solid mass, which is then extracted with 15 ml of toluene. The extraction solution has a dark brown color and is used directly in the metathesis catalysis of pentene-2.

Le ballon contenant la solution d'extraction est plongé dans un bain thermostatique à 25 °C. On injecte alors dans cette solution 3 ml de pentène-2 (mélange cis + trans). Après une heure de réaction, la conversion du pentène-2 est de 3 %. Après 4 jours de réaction, la conversion du pentène-2 est de 29 %. Les produits sont constitués uniquement par les butènes-2 cis et trans et les hexènes-3 cis et trans, dans un rapport molaire butènes : hexènes = 1:1.The flask containing the extraction solution is immersed in a thermostatic bath at 25 ° C. Then injected into this solution 3 ml of pentene-2 (cis + trans mixture). After one hour of reaction, the conversion of pentene-2 is 3%. After 4 days of reaction, the conversion of pentene-2 is 29%. The products consist solely of cis and trans butenes-2 and cis and trans hexenes-3, in a butene: hexene molar ratio = 1: 1.

EXEMPLE 10EXAMPLE 10 Préparation du catalyseur : Catalyst preparation :

Le bis-(di-t-butyl-2,6-méthyl-4-phénoxy)-isobutylaluminium est préparé selon le mode opératoire décrit dans l'exemple 1. Dans un ballon de 250 ml placé sous atmosphère d'argon et muni d'un barreau magnétique, on introduit 1 g d'heptoxyde de rhénium Re2O7 et 30 ml de diéthyléther. On refroidit la solution dans un bain de carboglace-acétone et on y ajoute en 5 minutes une solution de 2,16 g de bis-(di-t-butyl-2,6-méthyl-4-phénoxy)-isobutylaluminium dans 30 ml de diéthyléther. A la fin de l'addition, on laisse la température remonter à l'ambiante et on poursuit l'agitation pendant encore 2 heures. On évapore alors le solvant sous vide pour obtenir une masse solide brun foncé, que l'on extrait ensuite 3 fois par 30 ml de pentane. La solution d'extraction au pentane a une couleur brun-rouge et son évaporation à sec donne 2,66 g d'une poudre rouge foncé. Cette poudre est remise en solution dans 20 ml d'heptane.The bis- (di-t-butyl-2,6-methyl-4-phenoxy) -isobutylaluminum is prepared according to the procedure described in Example 1. In a 250 ml flask placed under an argon atmosphere and provided with 'a magnetic bar, 1 g of rhenium heptoxide Re 2 O 7 and 30 ml of diethyl ether are introduced. The solution is cooled in a dry ice-acetone bath and a solution of 2.16 g of bis- (di-t-butyl-2,6-methyl-4-phenoxy) -isobutylaluminum in 30 ml is added over 5 minutes. of diethyl ether. At the end of the addition, the temperature is allowed to rise to ambient and the stirring is continued for another 2 hours. The solvent is then evaporated under vacuum to obtain a dark brown solid mass, which is then extracted 3 times with 30 ml of pentane. The pentane extraction solution has a reddish brown color and its evaporation to dryness gives 2.66 g of a dark red powder. This powder is redissolved in 20 ml of heptane.

Utilisation en catalyse de métathèse du pentène-2 : Use in pentathin-2 metathesis catalysis :

On prélève 3 ml de la solution dans l'heptane du composé préparé ci-dessus, que l'on transfère dans un ballon de 100 ml placé sous atmosphère d'argon, équipé d'un barreau magnétique et plongé dans un bain thermostatique à 25 °C. On injecte alors dans le ballon 5 ml de pentène-2 (mélange cis + trans). Après 5 minutes de réaction, la conversion du pentène-2 est de 50 % (ce qui représente la conversion maximum à l'équilibre thermodynamique). Les produits sont constitués uniquement par les butènes-2 cis et trans et les hexènes-3 cis et trans.3 ml of the heptane solution of the compound prepared above are taken, which is transferred to a 100 ml flask placed under an argon atmosphere, equipped with a magnetic bar and immersed in a thermostatic bath at 25 ° C. 5 ml of pentene-2 are then injected into the balloon (cis + trans mixture). After 5 minutes of reaction, the conversion of pentene-2 is 50% (which represents the maximum conversion at thermodynamic equilibrium). The products consist only of butenes-2 cis and trans and hexenes-3 cis and trans.

EXEMPLE 11EXAMPLE 11 Préparation du catalyseur : Catalyst preparation :

Le bis-(di-t-butyl-2,6-méthyl-4-phénoxy)-isobutylaluminium est préparé selon le mode opératoire décrit dans l'exemple 1. Dans un ballon de 250 ml placé sous atmosphère d'argon et muni d'un barreau magnétique, on introduit 1 g d'heptoxyde de rhénium Re2O7 et 15 ml de diisopropyléther. On refroidit la solution dans un bain de carboglace-acétone et on y ajoute en 5 minutes une solution de 2,16 g de bis-(di-t-butyl-2,6-méthyl-4-phénoxy)-isobutylaluminium dans 30 ml de diisopropyléther. A la fin de l'addition, on laisse la température remonter à l'ambiante et on poursuit l'agitation pendant encore 2 heures. On évapore alors le solvant sous vide pour obtenir une masse solide brun foncé, que l'on extrait ensuite 4 fois par 20 ml de pentane. La solution d'extraction au pentane a une couleur brun-rouge et son évaporation à sec donne 2,48 g d'une poudre rouge foncé. Cette poudre est remise en solution dans 20 ml d'heptane.The bis- (di-t-butyl-2,6-methyl-4-phenoxy) -isobutylaluminum is prepared according to the procedure described in Example 1. In a 250 ml flask placed under an argon atmosphere and provided with 'a magnetic bar, 1 g of rhenium heptoxide Re 2 O 7 and 15 ml of diisopropyl ether are introduced. The solution is cooled in a dry ice-acetone bath and a solution of 2.16 g of bis- (di-t-butyl-2,6-methyl-4-phenoxy) -isobutylaluminum in 30 ml is added over 5 minutes. diisopropyl ether. At the end of the addition, the temperature is allowed to rise to ambient and the stirring is continued for another 2 hours. The solvent is then evaporated under vacuum to obtain a dark brown solid mass, which is then extracted 4 times with 20 ml of pentane. The pentane extraction solution has a reddish brown color and its evaporation to dryness gives 2.48 g of a dark red powder. This powder is redissolved in 20 ml of heptane.

Utilisation en catalyse de métathèse du pentène-2 : Use in pentathin-2 metathesis catalysis :

On prélève 3 ml de la solution dans l'heptane du composé préparé ci-dessus, que l'on transfère dans un ballon de 100 ml placé sous atmosphère d'argon, équipé d'un barreau magnétique et plongé dans un bain thermostatique à 25 °C. On injecte alors dans le ballon 5 ml de pentène-2 (mélange cis + trans). Après 2 minutes de réaction, la conversion du pentène-2 est de 47 % (la conversion maximum à l'équilibre thermodynamique est de 50 %). Les produits sont constitués uniquement par les butènes-2 cis et trans et les hexènes-3 cis et trans.3 ml of the heptane solution of the compound prepared above are taken, which is transferred to a 100 ml flask placed under an argon atmosphere, equipped with a magnetic bar and immersed in a thermostatic bath at 25 ° C. 5 ml of pentene-2 are then injected into the balloon (cis + trans mixture). After 2 minutes of reaction, the conversion of pentene-2 is 47% (the maximum conversion at thermodynamic equilibrium is 50%). The products consist only of butenes-2 cis and trans and hexenes-3 cis and trans.

Claims (22)

Composé de rhénium et d'aluminium de formule générale :

        O3Re-O-[Al(OR)(L)x-O]n-ReO3

dans laquelle R est un reste hydrocarbyle contenant de 1 à 40 atomes de carbone, n est un nombre entier de 1 à 10 et x est égal à 0 ou 1, L représentant le solvant de synthèse.Composed of rhenium and aluminum of general formula:

O 3 Re-O- [Al (OR) (L) x -O] n -ReO 3

in which R is a hydrocarbyl residue containing from 1 to 40 carbon atoms, n is an integer from 1 to 10 and x is equal to 0 or 1, L representing the synthesis solvent. Composé selon la revendication 1, dans lequel R est choisi dans le groupe formé par les restes alkyle, cycloalkyle, alkényle, aryle et, aryle ou cycloalkyle substitués par au moins un groupe alkyle.Compound according to Claim 1, in which R is chosen from the group formed by alkyl, cycloalkyl, alkenyl, aryl and, aryl or cycloalkyl radicals substituted by at least one alkyl group. Composé selon l'une des revendications précédentes, dans lequel R est choisi dans le groupe formé par les restes alkyle, cycloalkyle, alkényle, aryle et, aryle ou cycloalkyle substitués par au moins un groupe alkyle, lesdits restes étant substitués par au moins un groupe alkoxy ou au moins un halogène.Compound according to one of the preceding claims, in which R is chosen from the group formed by alkyl, cycloalkyl, alkenyl, aryl and, aryl or cycloalkyl radicals substituted by at least one alkyl group, said radicals being substituted by at least one group alkoxy or at least one halogen. Composé selon l'une des revendications précédentes, dans lequel R contient de 2 à 30 atomes de carbone.Compound according to one of the preceding claims, in which R contains from 2 to 30 carbon atoms. Composé selon l'une des revendications précédentes, dans lequel R est choisi dans le groupe formé par les restes éthyle, n-propyle, isopropyle, n-butyle, t-butyle, cyclohexyle, benzyle, diphénylméthyle, phényle, méthyl-2-phényle, méthyl-4-phényle, méthoxy-2-phényle, méthoxy-4-phényle, diméthyl-2,6-phényle, diisopropyl-2,6-phényle, t-butyl-2-phényle, t-butyl-2-méthyl-4-phényle, di-t-butyl-2,6-phényle, di-t-butyl-2,6-méthyl-4-phényle, tri-t-butyl-2,4,6-phényle, phényl-2-phényle, diphényl-2,6-phényle, fluoro-2-phényle, fluoro-4-phényle, pentafluorophényle.Compound according to one of the preceding claims, in which R is chosen from the group formed by ethyl, n-propyl, isopropyl, n-butyl, t-butyl, cyclohexyl, benzyl, diphenylmethyl, phenyl, methyl-2-phenyl radicals , methyl-4-phenyl, methoxy-2-phenyl, methoxy-4-phenyl, dimethyl-2,6-phenyl, diisopropyl-2,6-phenyl, t-butyl-2-phenyl, t-butyl-2-methyl -4-phenyl, di-t-butyl-2,6-phenyl, di-t-butyl-2,6-methyl-4-phenyl, tri-t-butyl-2,4,6-phenyl, phenyl-2 -phenyl, 2,6-diphenyl-phenyl, fluoro-2-phenyl, fluoro-4-phenyl, pentafluorophenyl. Composé selon l'une des revendications précédentes, dans lequel L est choisi dans le groupe constitué par les hydrocarbures aliphatiques, les hydrocarbures aromatiques, les hydrocarbures halogénés, les éthers, les sulfures.Compound according to one of the preceding claims, in which L is chosen from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers, sulfides. Procédé de préparation d'un composé selon l'une des revendications précédentes par mise en contact de l'heptoxyde de rhénium avec au moins un composé de l'aluminium de formule (RO)qAlR'r, dans laquelle R est un reste hydrocarbyle contenant de 1 à 40 atomes de carbone, R' est un reste alkyle contenant de 1 à 20 atomes de carbone et q et r sont égaux à 1 ou 2 avec q + r = 3.Process for the preparation of a compound according to one of the preceding claims by bringing rhenium heptoxide into contact with at least one aluminum compound of formula (RO) q AlR ' r , in which R is a hydrocarbyl residue containing from 1 to 40 carbon atoms, R 'is an alkyl residue containing from 1 to 20 carbon atoms and q and r are equal to 1 or 2 with q + r = 3. Procédé de préparation d'un composé selon l'une des revendications 1 à 6, par mise en contact de l'heptoxyde de rhénium avec au moins un composé de formule AlR'3 dans laquelle R' est un reste alkyle contenant de 1 à 20 atomes de carbone, et avec au moins un composé de formule ROH, R étant un reste hydrocarbyle contenant de 1 à 40 atomes de carbone, la réaction ayant lieu dans un solvant L.Process for the preparation of a compound according to one of Claims 1 to 6, by bringing rhenium heptoxide into contact with at least one compound of formula AlR ' 3 in which R' is an alkyl residue containing from 1 to 20 carbon atoms, and with at least one compound of formula ROH, R being a hydrocarbyl residue containing from 1 to 40 carbon atoms, the reaction taking place in a solvent L. Procédé selon l'une des revendications 7 ou 8 dans lequel la mise en contact est effectuée dans un solvant L choisi dans le groupe formé par les hydrocarbures aliphatiques, les hydrocarbures aromatiques, les hydrocarbures halogénés, les éthers, les sulfures.Process according to either of Claims 7 and 8, in which the contacting is carried out in a solvent L chosen from the group formed by aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers, sulphides. Procédé selon l'une des revendications 7 à 9, dans lequel le solvant L est anhydre.Method according to one of Claims 7 to 9, in which the solvent L is anhydrous. Procédé selon l'une des revendications 7 à 10, dans lequel le rapport molaire entre le composé d'aluminium et le rhénium est compris entre 0,2:1 et 10:1.Method according to one of claims 7 to 10, wherein the molar ratio between the aluminum compound and the rhenium is between 0.2: 1 and 10: 1. Procédé selon l'une des revendications 7 à 11, dans lequel le rapport molaire entre le composé d'aluminium et le rhénium est compris entre 0,5:1 et 5:1.Method according to one of Claims 7 to 11, in which the molar ratio between the aluminum compound and the rhenium is between 0.5: 1 and 5: 1. Procédé selon l'une des revendications 7 à 12, dans lequel la température est de -80 à 100 °C.Method according to one of Claims 7 to 12, in which the temperature is from -80 to 100 ° C. Procédé selon l'une des revendications 7 à 13, dans lequel la température est de -30 à 80 °C.Method according to one of Claims 7 to 13, in which the temperature is from -30 to 80 ° C. Procédé selon l'une des revendications 7 à 14, dans lequel R' contient 1 à 6 atomes de carbone.Method according to one of Claims 7 to 14, in which R 'contains 1 to 6 carbon atoms. Procédé selon l'une des revendications 7 et 9 à 15, comportant la préparation du composé (RO)qAlR'r puis la mise en contact dudit composé préalablement isolé avec l'heptoxyde de rhénium.Method according to one of claims 7 and 9 to 15, comprising the preparation of the compound (RO) q AlR ' r and then bringing said compound previously isolated into contact with rhenium heptoxide. Procédé selon l'une des revendications 7 à 16, comportant, après la mise en contact, l'élimination au moins en partie du solvant présent lors de ladite mise en contact et l'extraction du résidu obtenu par un autre solvant L1.Method according to one of claims 7 to 16, comprising, after contacting, at least partially removing the solvent present during said contacting and extracting the residue obtained with another solvent L 1 . Procédé selon la revendication 17, dans lequel l'autre solvant L1 est choisi dans le groupe formé par les hydrocarbures aliphatiques, les hydrocarbures cycloaliphatiques, les hydrocarbures aromatiques, les hydrocarbures halogénés, les dérivés nitrés.Process according to Claim 17, in which the other solvent L 1 is chosen from the group formed by aliphatic hydrocarbons, cycloaliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, nitro derivatives. Composé stable du rhénium et d'aluminium de formule générale :

        O3Re(L')-O-[Al(OR)(L)x-O]n-ReO3(L')

dans laquelle R est un reste hydrocarbyle contenant de 1 à 40 atomes de carbone, n est un nombre entier de 1 à 10, x est égal à 0 ou 1, L représentant le solvant de synthèse et L' est un ligand stabilisant choisi dans le groupe formé par les composés comportant au moins un atome d'oxygène, de soufre, d'azote, de phosphore ou d'arsenic.Stable rhenium and aluminum compound of general formula:

O 3 Re (L ') - O- [Al (OR) (L) x -O] n -ReO 3 (L')

in which R is a hydrocarbyl residue containing from 1 to 40 carbon atoms, n is an integer from 1 to 10, x is equal to 0 or 1, L representing the synthesis solvent and L 'is a stabilizing ligand chosen from the group formed by the compounds comprising at least one atom of oxygen, sulfur, nitrogen, phosphorus or arsenic. Composé selon la revendication 19 dans lequel L' est choisi dans le groupe constitué par les éthers, les sulfures, les amines, les phosphines.Compound according to Claim 19, in which L 'is chosen from the group consisting of ethers, sulphides, amines, phosphines. Utilisation d'un composé selon l'une des revendications 1 à 6 pour la préparation de catalyseurs.Use of a compound according to one of claims 1 to 6 for the preparation of catalysts. Utilisation d'un composé obtenu par le procédé de préparation selon l'une des revendications 7 à 18 pour la préparation de catalyseurs.Use of a compound obtained by the preparation process according to one of claims 7 to 18 for the preparation of catalysts.
EP95402429A 1994-11-04 1995-11-02 Rhenium and aluminium compounds, their preparation and their use as catalysts Expired - Lifetime EP0714902B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9413348A FR2726563B1 (en) 1994-11-04 1994-11-04 NOVEL RHENIUM AND ALUMINUM COMPOUNDS, THEIR PREPARATION AND THEIR USE AS CATALYSTS
FR9413348 1994-11-04

Publications (3)

Publication Number Publication Date
EP0714902A2 true EP0714902A2 (en) 1996-06-05
EP0714902A3 EP0714902A3 (en) 1997-05-02
EP0714902B1 EP0714902B1 (en) 2003-04-16

Family

ID=9468597

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95402429A Expired - Lifetime EP0714902B1 (en) 1994-11-04 1995-11-02 Rhenium and aluminium compounds, their preparation and their use as catalysts

Country Status (7)

Country Link
US (1) US5596115A (en)
EP (1) EP0714902B1 (en)
JP (1) JP3876350B2 (en)
KR (1) KR100399476B1 (en)
DE (1) DE69530356T2 (en)
FR (1) FR2726563B1 (en)
TW (1) TW287118B (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2726487B1 (en) * 1994-11-04 1996-12-13 Inst Francais Du Petrole CATALYTIC COMPOSITIONS BASED ON RHENIUM AND ALUMINUM COMPOUNDS, THEIR PREPARATION AND THEIR USE FOR OLEFIN METATHESIS
FR2740056B1 (en) * 1995-10-20 1997-12-05 Inst Francais Du Petrole SUPPORTED CATALYST CONTAINING RHENIUM AND ALUMINUM, PROCESS FOR PREPARATION AND APPLICATION TO OLEFIN METATHESIS
US6583329B1 (en) 1998-03-04 2003-06-24 Catalytic Distillation Technologies Olefin metathesis in a distillation column reactor
FR2789072B1 (en) * 1999-01-29 2001-04-13 Inst Francais Du Petrole PROCESS FOR THE METATHESIS OF OLEFINS IN THE PRESENCE OF A CATALYST STABILIZING AGENT
DE19962814A1 (en) 1999-12-23 2001-06-28 Targor Gmbh Catalyst system, useful for the production of polyolefins, comprises a metallocene, a Lewis base, a support and a compound containing at least one Group 3 element
DE10342150A1 (en) * 2003-09-12 2005-04-28 Degussa Process for the oxidation of organic substrates and catalyst composition for carrying out the process
US7220886B2 (en) * 2004-10-27 2007-05-22 Catalytic Distillation Technologies Olefin metathesis
CN101382659B (en) 2007-09-07 2010-09-29 鸿富锦精密工业（深圳）有限公司 A kind of total internal reflection prism system and its manufacturing method

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4454368A (en) * 1983-06-22 1984-06-12 Phillips Petroleum Company Olefin metathesis and catalyst
DE4009910A1 (en) * 1988-12-10 1991-10-02 Hoechst Ag Ethenolytic metathesis of olefin(s) - using organo-rhenium oxide catalyst on oxidic carrier
DE4006539A1 (en) * 1990-03-02 1991-09-05 Huels Chemische Werke Ag METHOD FOR THE METATHESIS OF OLEFINS AND FUNCTIONALIZED OLEFINS
US5135958A (en) * 1991-07-30 1992-08-04 Amoco Corporation Process for converting synthesis gas to paraffin wax
FR2740056B1 (en) * 1995-10-20 1997-12-05 Inst Francais Du Petrole SUPPORTED CATALYST CONTAINING RHENIUM AND ALUMINUM, PROCESS FOR PREPARATION AND APPLICATION TO OLEFIN METATHESIS

Also Published As

Publication number Publication date
TW287118B (en) 1996-10-01
DE69530356D1 (en) 2003-05-22
JPH08239396A (en) 1996-09-17
EP0714902A3 (en) 1997-05-02
JP3876350B2 (en) 2007-01-31
KR960017673A (en) 1996-06-17
FR2726563B1 (en) 1996-12-13
EP0714902B1 (en) 2003-04-16
DE69530356T2 (en) 2003-10-30
FR2726563A1 (en) 1996-05-10
KR100399476B1 (en) 2003-12-18
US5596115A (en) 1997-01-21

Similar Documents

Publication Publication Date Title
EP0710638B1 (en) Rhenium and aluminium containing catalytic compositions, their preparation and use for the metathesis of olefins
EP3368217A1 (en) Nickel-based catalytic composition in the presence of a specific activator and use thereof in a olefin oligomerisation method
CA2889602A1 (en) New nickel-based cyclic compound and its use in an olefin oligomerization process
EP2939743A1 (en) Novel nickel-based complexes and use thereof in a method for transforming olefins
EP1027357B1 (en) New compounds having one group 13 element, bound with one mono- or di-anionic trident ligand, a method of preparation and application thereof as polymerisation catalysts
EP0714902B1 (en) Rhenium and aluminium compounds, their preparation and their use as catalysts
EP1392708B1 (en) Method for preparing metallic carbene-based catalysts for hydrosilylation of unsaturated compounds and resulting catalysts
EP2939744A1 (en) Novel nickel-based cyclic complexes and use thereof in a method for transforming olefins
EP0710639B1 (en) New supported compounds containing rhenium and aluminium, their preparation and use for the metathesis of olefins
WO2019207246A1 (en) Method for olefin metathesis by means of an acid-activated catalyst
EP0191260B1 (en) Pentacoordinated silicon complexes, process for their preparation and their use in preparing organosilanes
EP0196253B1 (en) Catalytic system, its preparation method and its use in the production of aldehydes
EP0161979B1 (en) Process for dimerizung a conjugated diene
EP0335765B1 (en) Catalytic system, its preparation process and use for preparing aldehyds
EP0002142B1 (en) Complexes of boranes, their preparation, and their use in hydroboration and reduction reactions
EP0647218B1 (en) Method for metathetically preparing sulphur-containing polymers or organic compounds
JP2001514184A (en) Production of ruthenium complex
FR2793792A1 (en) PROCESS FOR ALPHA-METALLATION OF A HETEROCYCLIC, MONOCYCLIC OR POLYCYCLIC DERIVATIVE AND HAVING AT LEAST ONE HATEROCYCLE WITH 5 ATOMS, UNSATURATED OR AROMATIC
FR2704859A1 (en) Process for the preparation of nickel (II) complexes containing a hetero-difunctional ligand and ethylene polymerization process with the complexes thus obtained
FR2724650A1 (en) Dimerisation, co-dimerisation and oligomerisation of olefins
FR2499558A1 (en) Metathesis of unsatd. organic cpds. with terminal functional Gps. - using molybdenum or tungsten catalyst and silane co-catalyst
FR2855175A1 (en) Production of indium carboxylate or carboxylate-halide for use e.g. as Lewis acid co-catalyst, involves reacting indium halide with alkali metal or ammonium carboxylate in anhydrous polar aprotic solvent
EP3463653A1 (en) Catalytic composition comprising chromium and a phosphine-based ligand, and use thereof in an octene production method
FR2784675A1 (en) PROCESS FOR RECOVERING AMMONIUM OR QUATERNARY PHOSPHONIUM HALIDES
BE861092A (en) CATALYSTS FOR THE POLYMERIZATION OF OLEFINS

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): DE GB IT NL

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): DE GB IT NL

17P Request for examination filed

Effective date: 19971103

17Q First examination report despatched

Effective date: 20001005

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): DE GB IT NL

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20030416

REF Corresponds to:

Ref document number: 69530356

Country of ref document: DE

Date of ref document: 20030522

Kind code of ref document: P

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20040119

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20081125

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20081120

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20081119

Year of fee payment: 14

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20100601

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20091102

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100601

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091102

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20101201

Year of fee payment: 16

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091102

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 69530356

Country of ref document: DE

Owner name: IFP ENERGIES NOUVELLES, FR

Free format text: FORMER OWNER: INSTITUT FRANCAIS DU PETROLE, RUEIL-MALMAISON, FR

Effective date: 20110331

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69530356

Country of ref document: DE

Effective date: 20130601

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130601